U.S. patent application number 12/874452 was filed with the patent office on 2011-03-10 for process for the synthesis of fluorinated ethers of aromatic acids.
This patent application is currently assigned to E. I. DU PONT DE NEMOURS AND COMPANY. Invention is credited to Neville Everton Drysdale, Surbhi Mahajan Du, Kenneth Gene Moloy, Joel M. Pollino, Joachim C. Ritter.
Application Number | 20110060116 12/874452 |
Document ID | / |
Family ID | 43648249 |
Filed Date | 2011-03-10 |
United States Patent
Application |
20110060116 |
Kind Code |
A1 |
Drysdale; Neville Everton ;
et al. |
March 10, 2011 |
PROCESS FOR THE SYNTHESIS OF FLUORINATED ETHERS OF AROMATIC
ACIDS
Abstract
New fluorinated ethers of aromatic acids and diesters are
disclosed. These compositions can be applied to, e.g., fibers,
yarns, carpets, garments, films, molded parts, paper and cardboard,
stone, and tile to impart soil, water and oil resistance. By
incorporating the fluorinated ethers of aromatic acids, or diesters
thereof, into polymer backbones, more lasting soil, water and oil
resistance, as well as improved flame retardance, can be
achieved.
Inventors: |
Drysdale; Neville Everton;
(Newark, DE) ; Mahajan Du; Surbhi; (Newark,
DE) ; Moloy; Kenneth Gene; (Hockessin, DE) ;
Pollino; Joel M.; (Elkton, MD) ; Ritter; Joachim
C.; (Wilmington, DE) |
Assignee: |
E. I. DU PONT DE NEMOURS AND
COMPANY
Wilmington
DE
|
Family ID: |
43648249 |
Appl. No.: |
12/874452 |
Filed: |
September 2, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61239107 |
Sep 2, 2009 |
|
|
|
Current U.S.
Class: |
528/206 ; 560/62;
562/472 |
Current CPC
Class: |
C07C 69/82 20130101;
C07C 69/80 20130101; C07C 65/24 20130101 |
Class at
Publication: |
528/206 ; 560/62;
562/472 |
International
Class: |
C08G 65/38 20060101
C08G065/38; C07C 69/80 20060101 C07C069/80; C07C 59/315 20060101
C07C059/315 |
Claims
1. A compound as represented by the structure of the following
Formula I: ##STR00036## wherein: Ar is a C.sub.6.about.C.sub.20
monocyclic or polycyclic aromatic nucleus, n and m are each
independently a nonzero value, n+m is less than or equal to 8,
R.sub.f is a fluorinated alkyl, alkaryl, aralkyl or aryl group,
optionally containing one or more ether linkages --O--; and R is H
or a branched or linear C.sub.1 to 10 alkyl group.
2. A compound according to claim 1 wherein R.sub.f is selected from
the group consisting of: CF.sub.3
(CF.sub.2).sub.a(CH.sub.2).sub.b--, wherein a=an integer from 0 to
15 and b=1, 3 or 4; HCF.sub.2(CF.sub.2).sub.c(CH.sub.2).sub.d--
wherein c=an integer from 0 to 15 and d=1, 3, or 4;
CF.sub.3CF.sub.2CF.sub.2OCFHCF.sub.2(OCH.sub.2CH.sub.2).sub.e-- and
CF.sub.3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2(OCH.sub.2CH.sub.2).sub.e--,
wherein e=an integer from 1 to 12; (CF.sub.3).sub.2CH--,
(CF.sub.3CF.sub.2CFH)(F)(CF.sub.3)C--,
(CF.sub.3CF.sub.2CFH)(F)(CF.sub.3)CCH.sub.2--,
(CF.sub.3).sub.2(H)C(CF.sub.3CF.sub.2)(F)C--, (CF.sub.3).sub.2
(H)C(CF.sub.3CF.sub.2)(F)CCH.sub.2--, pentafluorophenyl,
CF.sub.3(CF.sub.2).sub.f(CH.sub.2).sub.2-- wherein f=an integer
from 0 to 15, HCF.sub.2(CF.sub.2).sub.g (CH.sub.2).sub.h-- wherein
g=an integer from 0 to about 15 and h=0 or 2,
CF.sub.3CF.sub.2CF.sub.2OCFHCF.sub.2--,
CF.sub.3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2--,
CF.sub.3CF.sub.2(CH.sub.2CH.sub.2CF.sub.2CF.sub.2).sub.iCH.sub.2CH.sub.2--
-,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2(CH.sub.2CH.sub.2CF.sub.2CF.sub.2).sub.-
iCH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2(CH.sub.2CF.sub.2).sub.iCH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2(CH.sub.2CF.sub.2).sub.iCH.sub.2CH.sub.2--
-, wherein i=an integer from 1 to 6, and CF.sub.3CFHCF.sub.2--.
3. A compound as represented by the structure of the following
Formula II: ##STR00037## wherein R.sub.f is a fluorinated alkyl,
alkaryl, aralkyl or aryl group, optionally containing one or more
ether linkages --O--; and R is H or a branched or linear C.sub.1 to
10 alkyl group.
4. A compound according to claim 3 wherein R.sub.f is selected from
the group consisting of:
CF.sub.3(CF.sub.2).sub.a(CH.sub.2).sub.b--, wherein a=an integer
from 0 to 15 and b=1, 3 or 4;
HCF.sub.2(CF.sub.2).sub.c(CH.sub.2).sub.d-- wherein c=an integer
from 0 to 15 and d=1, 3, or 4;
CF.sub.3CF.sub.2CF.sub.2OCFHCF.sub.2(OCH.sub.2CH.sub.2).sub.e-- and
CF.sub.3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2(OCH.sub.2CH.sub.2).sub.e--,
wherein e=an integer from 1 to 12; (CF.sub.3).sub.2CH--,
(CF.sub.3CF.sub.2CFH)(F)(CF.sub.3)C--,
(CF.sub.3CF.sub.2CFH)(F)(CF.sub.3)CCH.sub.2--,
(CF.sub.3).sub.2(H)C(CF.sub.3CF.sub.2)(F)C--,
(CF.sub.3).sub.2(H)C(CF.sub.3CF.sub.2)(F)CCH.sub.2--,
pentafluorophenyl, CF.sub.3(CF.sub.2).sub.f(CH.sub.2).sub.2--
wherein f=an integer from 0 to 15,
HCF.sub.2(CF.sub.2).sub.g(CH.sub.2).sub.h-- wherein g=an integer
from 0 to about 15 and h=0 or 2,
CF.sub.3CF.sub.2CF.sub.2OCFHCF.sub.2--,
CF.sub.3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2--,
CF.sub.3CF.sub.2(CH.sub.2CH.sub.2CF.sub.2CF.sub.2).sub.iCH.sub.2CH.sub.2--
-,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2(CH.sub.2CH.sub.2CF.sub.2CF.sub.2).sub.-
iCH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2(CH.sub.2CF.sub.2).sub.iCH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2(CH.sub.2CF.sub.2).sub.iCH.sub.2CH.sub.2--
-, wherein i=an integer from 1 to 6, and CF.sub.3CFHCF.sub.2--.
5. A compound as represented by the structure of the following
Formula III: ##STR00038## wherein R.sub.f is a fluorinated alkyl,
alkaryl, aralkyl or aryl group, optionally containing one or more
ether linkages --O--; and R is H or a branched or linear C.sub.1 to
10 alkyl group.
6. A compound according to claim 5 wherein R.sub.f is selected from
the group consisting of:
CF.sub.3(CF.sub.2).sub.a(CH.sub.2).sub.b--, wherein a=an integer
from 0 to 15 and b=1, 3 or 4;
HCF.sub.2(CF.sub.2).sub.c(CH.sub.2).sub.d-- wherein c=an integer
from 0 to 15 and d=1, 3, or 4;
CF.sub.3CF.sub.2CF.sub.2OCFHCF.sub.2(OCH.sub.2CH.sub.2).sub.e-- and
CF.sub.3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2(OCH.sub.2CH.sub.2).sub.e--,
wherein e=an integer from 1 to 12; (CF.sub.3).sub.2CH--,
(CF.sub.3CF.sub.2CFH)(F)(CF.sub.3)C--,
(CF.sub.3CF.sub.2CFH)(F)(CF.sub.3)CCH.sub.2--,
(CF.sub.3).sub.2(H)C(CF.sub.3CF.sub.2)(F)C--,
(CF.sub.3).sub.2(H)C(CF.sub.3CF.sub.2)(F)CCH.sub.2--,
pentafluorophenyl, CF.sub.3(CF.sub.2).sub.f(CH.sub.2).sub.2--
wherein f=an integer from 0 to 15,
HCF.sub.2(CF.sub.2).sub.g(CH.sub.2).sub.h-- wherein g=an integer
from 0 to about 15 and h=0 or 2,
CF.sub.3CF.sub.2CF.sub.2OCFHCF.sub.2--,
CF.sub.3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2--,
CF.sub.3CF.sub.2(CH.sub.2CH.sub.2CF.sub.2CF.sub.2).sub.iCH.sub.2CH.sub.2--
-,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2(CH.sub.2CH.sub.2CF.sub.2CF.sub.2).sub.-
iCH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2(CH.sub.2CF.sub.2).sub.iCH.sub.2CH.sub.2--,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2(CH.sub.2CF.sub.2).sub.iCH.sub.2CH.sub.2--
-, wherein i=an integer from 1 to 6, and CF.sub.3CFHCF.sub.2--.
7. A monomer, oligomer or polymer that comprises a compound
according to claim 1.
8. A monomer, oligomer or polymer according to claim 7 that
comprises one or more functionalities selected from the group
consisting of ester functionality, ether functionality, amide
functionality, imide functionality, imidazole functionality,
thiazole functionality, oxazole functionality, carbonate
functionality, acrylate functionality, epoxide functionality,
urethane functionality, acetal functionality, and anhydride
functionality.
9. An article of manufacture that comprises a compound according to
claim 1.
10. An article of manufacture that comprises a monomer, oligomer or
polymer according to claim 8.
11. An article according to claim 9 which is fabricated as fiber,
yarn, carpet, a garment, a film, a molded part, paper, cardboard,
stone or tile.
12. An article according to claim 10 which is fabricated as fiber,
yarn, carpet, a garment, a film, a molded part, paper, cardboard,
stone or tile.
Description
[0001] This application claims priority under 35 U.S.C.
.sctn.119(e) from, and claims the benefit of, U.S. Provisional
Application No. 61/239,107, filed Sep. 2, 2009, which is by this
reference incorporated in its entirety as a part hereof for all
purposes.
TECHNICAL FIELD
[0002] This invention relates to the manufacture of fluorinated
ethers of aromatic acids or hydroxy aromatic acids, which are
valuable for a variety of purposes such as use as surfactants,
intermediates or as monomers to make polymers.
BACKGROUND
[0003] Fluorinated organic compounds have been used in a wide
variety of applications, for example, in surface treatments, as
intermediates in the synthesis of compounds such as
pharmaceuticals, and as monomers in the synthesis of polymers with
highly valued properties. In particular, as compounds or as
components of polymers, they are used to impart soil, water and oil
resistance, and improved flame retardancy to materials, especially
in fiber-related industries. Generally, the fluorinated compounds
are applied as a topical treatment, but their effectiveness
decreases over time because of material loss resulting from wear
and washing.
[0004] A need thus remains to provide polymeric materials that have
improved, more durable soil and oil resistance.
SUMMARY
[0005] Provided herein are new compositions or compounds as
represented by the structure of the following Formula I:
##STR00001##
wherein: [0006] Ar is a C.sub.6.about.C.sub.20 monocyclic or
polycyclic aromatic nucleus, [0007] n and m are each independently
a nonzero value, [0008] n+m is less than or equal to 8, [0009]
R.sub.f is a fluorinated alkyl, alkaryl, aralkyl, or aryl group,
optionally containing one or more ether linkages --O--; and [0010]
R is H or a branched or linear C.sub.1 to 10 alkyl group.
[0011] Another embodiment of this invention provides a process for
preparing a compound, monomer, oligomer or polymer by preparing a
fluorinated ether of an aromatic acid as is represented by the
structure of Formula I, and then subjecting the ether so produced
to a reaction (including a multi-step reaction) to prepare
therefrom a compound, monomer, oligomer or polymer.
[0012] It has been found that by incorporating fluorinated aromatic
diesters into polymer backbones, more lasting soil, water and oil
resistance, as well as improved flame retardance, can be achieved
in fiber-related products made therefrom.
DETAILED DESCRIPTION
[0013] This disclosure provides new compositions or compounds as
represented by the structure of the following Formula I:
##STR00002##
wherein:
[0014] Ar is a C.sub.6.about.C.sub.20 monocyclic or polycyclic
aromatic nucleus,
[0015] n and m are each independently a nonzero value,
[0016] n+m is less than or equal to 8,
[0017] R.sub.f is a fluorinated alkyl, alkaryl, aralkyl, or aryl
group, optionally containing one or more ether linkages --O--;
and
[0018] R is H or a branched or linear C.sub.1 to 10 alkyl
group.
[0019] Examples of R.sub.f groups as used in the above Formula I
include without limitation:
[0020] CF.sub.3(CF.sub.2).sub.a(CH.sub.2).sub.b-- wherein a=an
integer from 0 to 15 and b=1, 3 or 4;
[0021] HCF.sub.2(CF.sub.2).sub.c(CH.sub.2).sub.d-- wherein c=an
integer from 0 to 15 and d=1, 3, or 4;
[0022]
CF.sub.3CF.sub.2CF.sub.2OCFHCF.sub.2(OCH.sub.2CH.sub.2).sub.e--
and
[0023]
CF.sub.3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2(OCH.sub.2CH.sub.2).sub.e--
-, wherein e=an integer from 1 to 12;
[0024] (CF.sub.3).sub.2CH--,
[0025] (CF.sub.3CF.sub.2CFH)(F)(CF.sub.3)C--,
[0026] (CF.sub.3CF.sub.2CFH)(F)(CF.sub.3)CCH.sub.2--,
[0027] (CF.sub.3).sub.2(H)C(CF.sub.3CF.sub.2)(F)C--,
[0028] (CF.sub.3).sub.2(H)C(CF.sub.3CF.sub.2)(F)CCH.sub.2--,
[0029] pentafluorophenyl,
[0030] CF.sub.3(CF.sub.2).sub.f(CH.sub.2).sub.2-- wherein f=an
integer from 0 to 15, HCF.sub.2(CF.sub.2).sub.g(CH.sub.2).sub.h--
wherein g=an integer from 0 to about 15 and h=0 or 2,
[0031] CF.sub.3CF.sub.2CF.sub.2OCFHCF.sub.2--,
[0032] CF.sub.3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2--,
[0033]
CF.sub.3CF.sub.2(CH.sub.2CH.sub.2CF.sub.2CF.sub.2).sub.iCH.sub.2CH.-
sub.2--,
[0034]
CF.sub.3CF.sub.2CF.sub.2CF.sub.2(CH.sub.2CH.sub.2CF.sub.2CF.sub.2).-
sub.iCH.sub.2CH.sub.2--,
[0035]
CF.sub.3CF.sub.2(CH.sub.2CF.sub.2).sub.iCH.sub.2CH.sub.2--,
[0036]
CF.sub.3CF.sub.2CF.sub.2CF.sub.2(CH.sub.2CF.sub.2).sub.iCH.sub.2CH.-
sub.2--, wherein i=an integer from 1 to 6; and
[0037] CF.sub.3CFHCF.sub.2--.
[0038] As used herein, the term "alkyl" denotes a univalent group
derived from an alkane by removing a hydrogen atom from any carbon
atom: --C.sub.xH.sub.2x+1 where x.gtoreq.1.
[0039] As used herein, the term "aryl" denotes a univalent group
whose free valence is to a carbon atom of an aromatic ring.
[0040] As used herein, the term "aralkyl" denotes an alkyl group
which bears an aryl group. One such example is the benzyl group,
i.e. the radical,
##STR00003##
[0041] As used herein, the term "alkaryl" denotes an aryl group
which bears an alkyl group. Some examples are the 4-methylphenyl
radical,
##STR00004##
the mesityl group (i.e. 2,4,6-trimethylphenyl) and the
2,6-diisopropylphenyl group (i.e., the
(CH.sub.3CHCH.sub.3).sub.2C.sub.6H.sub.3-radical).
[0042] The radical denoted by
##STR00005##
is an n+m valent C.sub.6.about.C.sub.20 monocyclic or polycyclic
aromatic nucleus formed by the removal of n+m hydrogens from
different carbon atoms on the aromatic ring, or on the aromatic
rings when the structure is polycyclic. The radical "Ar" may be
substituted or unsubstituted; when unsubstituted, it contains only
carbon and hydrogen.
[0043] One example of a suitable Ar group is phenylene, as shown
below, wherein n=m=1.
##STR00006##
A preferred Ar group is shown below, wherein n=m=2.
##STR00007##
[0044] In one embodiment of this invention, new compositions or
compounds as represented by the structure of the following Formula
II
##STR00008##
are provided. In this compound, Ar is
##STR00009##
n=m=2.
[0045] In another embodiment of this invention, new compositions or
compounds as represented by the structure of the following Formula
III
##STR00010##
are provided. In this compound, Ar is
##STR00011##
n=1, and m=2.
[0046] When R is H and R.sub.f is not attached to the ether oxygen
in Formula I via a CF.sub.2 group or a CF.sub.2CH.sub.2CH.sub.2
group, compositions of Formula I can be made by the following
copper-catalyzed process:
[0047] (a) contacting a halogenated aromatic acid that is described
by the structure of Formula IV
##STR00012##
wherein each X is independently Cl, Br, or I, and Ar, n and m are
as set forth above, with [0048] (i) a total of from about n+m to
about n+m+1 equivalents of the alcoholate RfO.sup.-M.sup.+ (wherein
M is Na or K) per equivalent of halogenated aromatic acid, in a
polar aprotic solvent or in RfOH as a solvent; [0049] (ii) a copper
(I) or copper (II) source; and [0050] (iii) a ligand that
coordinates to copper, wherein said ligand is a diamine, diketones,
Schiff Base, or amino acid, to form a reaction mixture;
[0051] (b) heating the reaction mixture to form the m-basic salt of
the product of step (a), as described by the structure of Formula
V;
##STR00013##
[0052] (c) optionally, separating the Formula V m-basic salt from
the reaction mixture in which it is formed; and
[0053] (d) contacting the Formula V m-basic salt with acid to form
therefrom a fluorinated ether of an aromatic acid.
[0054] An "m-basic salt", as the term is used herein, is the salt
formed from an acid that contains in each molecule m acid groups
having a replaceable hydrogen atom.
[0055] Examples of R.sub.f groups that are not attached to the
ether oxygen in Formula I via a CF.sub.2 group or a
CF.sub.2CH.sub.2CH.sub.2 group include without limitation:
[0056] CF.sub.3(CF.sub.2).sub.a(CH.sub.2).sub.b-- wherein a=an
integer from 0 to 15 and b=1, 3 or 4;
[0057] HCF.sub.2(CF.sub.2).sub.c(CH.sub.2).sub.d-- wherein c=an
integer from 0 to 15 and d=1, 3, or 4;
[0058]
CF.sub.3CF.sub.2CF.sub.2OCFHCF.sub.2(OCH.sub.2CH.sub.2).sub.e--
and
[0059]
CF.sub.3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2(OCH.sub.2CH.sub.2).sub.e--
-, wherein e=an integer from 1 to 12;
[0060] (CF.sub.3).sub.2CH--,
[0061] (CF.sub.3CF.sub.2CFH)(F)(CF.sub.3)C--,
[0062] (CF.sub.3CF.sub.2CFH)(F)(CF.sub.3)CCH.sub.2--,
[0063] (CF.sub.3).sub.2(H)C(CF.sub.3CF.sub.2)(F)C--,
[0064] (CF.sub.3).sub.2(H)C(CF.sub.3CF.sub.2)(F)CCH.sub.2--;
and
[0065] pentafluorophenyl.
[0066] Various halogenated aromatic acids, to be used as a starting
material in a copper-cartalyzed process to make compositions of
Formula I wherein R.dbd.H and R.sub.f is not attached to the ether
oxygen via a CF.sub.2 group or a CF.sub.2CH.sub.2CH.sub.2 group,
are commercially available. For example, 2-bromobenzoic acid is
available from Aldrich Chemical Company (Milwaukee, Wis.). It can
be synthesized, however, by oxidation of bromomethylbenzene as
described in Sasson et al, Journal of Organic Chemistry (1986),
51(15), 2880-2883. Other halogenated aromatic acids that can be
used include without limitation 2,5-dibromobenzoic acid,
2-bromo-5-nitrobenzoic acid, 2-bromo-5-methylbenzoic acid,
2-chlorobenzoic acid, 2,5-dichlorobenzoic acid,
2-chloro-3,5-dinitrobenzoic acid, 2-chloro-5-methylbenzoic acid,
2-bromo-5-methoxybenzoic acid, 5-bromo-2-chlorobenzoic acid,
2,3-dichlorobenzoic acid, 2-chloro-4-nitrobenzoic acid,
2,5-dichloroterephthalic acid, 2-chloro-5-nitrobenzoic acid,
2,5-dibromoterephthalic acid, and 2,5-dichloroterephthalic acid,
all of which are commercially available. Preferably, the
halogenated aromatic acid is 2,5-dibromoterephthalic acid or
2,5-dichloroterephthalic acid.
[0067] Other halogenated aromatic acids useful as a starting
material in a copper catalyzed process include those shown in the
left column of the table below, wherein X.dbd.Cl, Br or I, and
wherein the corresponding ether of an aromatic acid produced
therefrom by the process of this invention is shown in the right
column:
TABLE-US-00001 (COOH).sub.m--Ar--(X).sub.n
(COOH).sub.m--Ar--(OR.sub.f).sub.n ##STR00014## ##STR00015##
##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020##
##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025##
##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030##
##STR00031##
[0068] The copper source is a Cu(I) salt, a Cu(II) salt, or
mixtures thereof. Examples include without limitation CuCl, CuBr,
CuI, Cu.sub.2SO.sub.4, CuNO.sub.3, CuCl.sub.2, CuBr.sub.2,
CuI.sub.2, CuSO.sub.4, and Cu(NO.sub.3).sub.2. The selection of the
copper source may be made in relation to the identity of the
halogenated aromatic acid used. For example, if the starting
halogenated aromatic acid is a bromobenzoic acid, CuCl, CuBr, CuI,
Cu.sub.2SO.sub.4, CuNO.sub.3, CuCl.sub.2, CuBr.sub.2, CuI.sub.2,
CuSO.sub.4, and Cu(NO.sub.3).sub.2 will be included among the
useful choices. If the starting halogenated aromatic acid is a
chlorobenzoic acid, CuBr, CuI, CuBr.sub.2 and CuI.sub.2 will be
included among the useful choices.
[0069] The copper-catalyzed processes for making a compound hereof
are described in greater detail in copending U.S. Provisional
Patent Applications 61/239,102, 61/239,103, 61/239,106, and
61/239,194, each of which is by this reference incorporated in its
entirety as a part hereof for all purposes.
[0070] Compositions described by Formula I wherein (1) R is not H,
or (2) R is H and R.sub.f is attached to the ether oxygen in
Formula I via a CF.sub.2 group or a CF.sub.2CH.sub.2CH.sub.2 group,
can be made using synthetic routes other than the copper-catalyzed
processes described above. Examples of such R.sub.f groups include
without limitation:
[0071] CF.sub.3(CF.sub.2).sub.f(CH.sub.2).sub.2-- wherein f=an
integer from 0 to 15,
[0072] HCF.sub.2(CF.sub.2).sub.g(CH.sub.2).sub.h-- wherein g=an
integer from 0 to about 15 and h=0 or 2,
[0073] CF.sub.3CF.sub.2CF.sub.2OCFHCF.sub.2--,
[0074] CF.sub.3CF.sub.2CF.sub.2OCF.sub.2CF.sub.2--,
[0075]
CF.sub.3CF.sub.2(CH.sub.2CH.sub.2CF.sub.2CF.sub.2).sub.iCH.sub.2CH.-
sub.2--,
[0076]
CF.sub.3CF.sub.2CF.sub.2CF.sub.2(CH.sub.2CH.sub.2CF.sub.2CF.sub.2).-
sub.iCH.sub.2CH.sub.2--,
[0077]
CF.sub.3CF.sub.2(CH.sub.2CF.sub.2).sub.iCH.sub.2CH.sub.2--,
[0078]
CF.sub.3CF.sub.2CF.sub.2CF.sub.2(CH.sub.2CF.sub.2).sub.iCH.sub.2CH.-
sub.2--, wherein i=an integer from 1 to 6; and
[0079] CF.sub.3CFHCF.sub.2--.
[0080] Such compositions can be prepared, for example, by the
addition of a phenol to a fluorinated olefin. Such reactions are
described, for example, in Feiring and Wonchoba, Journal of Organic
Chemistry (1992), 57(26), 7014-17; U.S. Pat. No. 5,198,570; U.S.
Patent Publication No. 2005/065382; and Furin et al, Journal of
Fluorine Chemistry (2000), 106(1), 13-24. For example, in order to
prepare a composition described by Formula III wherein Rf is
CF.sub.2HCF.sub.2--, one would react the appropriate phenol with
tetrafluoroethylene in the presence of base in a polar solvent or
solvent mixture:
##STR00032##
[0081] Alternatively, the compositions can be made by the coupling
of alcohols and phenols to form aryl ethers using
triphenylphosphine and diethyl azodicarboxylate ("DEAD"). One
scheme is shown below (Example 3):
##STR00033##
[0082] This is a version of the Mitsunobu Reaction, as described
for example in Mundy, Bradford P. et al, Name Reactions and
Reagents in Organic Synthesis, 2nd Edition, John Wiley & Sons,
Hoboken, N.J. (2005). The Mitsunobu Reaction was applied to the
preparation of fluorinated aryl ethers by A. V. Malkov et al
[Journal of Organic Chemistry (2007), 72(4), 1315-1325].
[0083] The compositions or compounds of the above Formula I can be
applied, for example, to fibers, yarns, carpets, garments, films,
molded parts, paper and cardboard, stone, and tile to impart soil,
water and oil resistance thereto. By incorporating the fluorinated
ethers of aromatic acids, or diesters thereof, into polymer
backbones, however, more lasting soil, water and oil resistance, as
well as improved flame retardance, can be achieved.
[0084] Compositions or compounds of Formula I as prepared herein
can thus be used in turn in the synthesis of products such as a
compound, a monomer, or an oligomer or polymer thereof. These
produced materials may have one or more of ester functionality,
ether functionality, amide functionality, imide functionality,
imidazole functionality, thiazole functionality, oxazole
functionality, carbonate functionality, acrylate functionality,
epoxide functionality, urethane functionality, acetal
functionality, or anhydride functionality.
[0085] A Formula I compound may, as desired, be isolated and
recovered as described above. It may also be subjected with or
without recovery from the reaction mixture to further steps to
convert it to another product such as another compound (e.g. a
monomer), or an oligomer or a polymer. Another embodiment of a
process hereof thus provides a process for converting a Formula I
compound, through one or more reactions, into another compound, or
into an oligomer or a polymer. A Formula I compound may be made by
a process such as described above, and then may be subjected, for
example, to a polymerization reaction to prepare an oligomer or
polymer therefrom, such as those having ester functionality or
amide functionality, or a
pyridobisimidazole-2,6-diyl(2,5-dihydroxy-p-phenylene) polymer.
[0086] The compounds of Formula I made by the process disclosed
herein, in particular the dimethyl esters, can be used in
condensation polymerizations to produce fluorinated condensation
polymers, e.g. those including without limitation polyesters,
polyamides, polyimides, and polybenzimidazoles. Representative
reactions involving a material of this invention, or a derivative
of such material, such as a diester, include, for example, making a
polyester from one or more compounds of Formula I and either
diethylene glycol or triethylene glycol in the presence of 0.1% of
Zn.sub.3(BO.sub.3).sub.2 in 1-methylnaphthalene under nitrogen,
according to the method taught in U.S. Pat. No. 3,047,536 (which is
incorporated in its entirety as a part hereof for all purposes).
Similarly, a fluorinated ether of aromatic acid is suitable for
copolymerization with a dibasic acid and a glycol to prepare a
heat-stabilized fluorinated polyester according to the method
taught in U.S. Pat. No. 3,227,680 (which is incorporated in its
entirety as a part hereof for all purposes), wherein representative
conditions involve forming a prepolymer in the presence of titanium
tetraisopropoxide in butanol at 200.about.250.degree. C., followed
by solid-phase polymerization at 280.degree. C. at a pressure of
0.08 mm Hg.
[0087] Other diols useful to make a polyester from a Formula I
compound are those that are derived from a fermentation process,
and another embodiment of this invention thus involves a process
for making from a Formula I compound an oligomer or polymer that
further includes a step of providing a diol to such a process from
a fermentation process.
[0088] A Formula I compound may be converted into a polyamide
oligomer or polymer by reaction with a diamine in a process in
which, for example, the polymerization takes place in solution in
an organic compound that is liquid under the conditions of the
reaction, is a solvent for both the Formula I compound and the
diamine, and has a swelling or partial salvation action on the
polymeric product. The reaction may be effected at moderate
temperatures, e.g. under 100.degree. C., and is preferably effected
in the presence of an acid acceptor that is also soluble in the
chosen solvent. Suitable solvents include methyl ethyl ketone,
acetonitrile, N,N-dimethylacetamide dimethyl formamide containing
5% lithium chloride, and N-methylpyrrolidone containing a
quaternary ammonium chloride such as methyl tri-n-butyl ammonium
chloride or methyl-tri-n-propyl ammonium chloride. Combination of
the reactant components causes generation of considerable heat and
the agitation, also, results in generation of heat energy. For that
reason, the solvent system and other materials are cooled at all
times during the process when cooling is necessary to maintain the
desired temperature. Processes similar to the foregoing are
described in U.S. Pat. No. 3,554,966; U.S. Pat. No. 4,737,571; and
CA 2,355,316.
[0089] A Formula I compound may also be converted into a polyamide
oligomer or polymer by reaction with a diamine in a process in
which, for example, a solution of the diamine in a solvent may be
contacted in the presence of an acid acceptor with a solution of
the Formula I compound in a second solvent that is immiscible with
the first to effect polymerization at the interface of the two
phases. The diamine may, for example, be dissolved or dispersed in
a water containing base with the base being used in sufficient
quantities to neutralize the acid generated during polymerization.
Sodium hydroxide may be used as the acid acceptor. Preferred
solvents for the diacid(halide) are tetrachloroethylene,
methylenechloride, naphtha and chloroform. The solvent for the
Formula I compound should be a relative non-solvent for the amide
reaction product, and be relatively immiscible in the amine
solvent. A preferred threshold of immiscibility is as follows: an
organic solvent should be soluble in the amine solvent not more
than between 0.01 weight percent and 1.0 weight percent. The
diamine, base and water are added together and vigorously stirred.
High shearing action of the stirrer is important. The solution of
acid chloride is added to the aqueous slurry. Contacting is
generally carried out at from 0.degree. C. to 60.degree. C., for
example, for from about 1 second to 10 minutes, and preferably from
5 seconds to 5 minutes at room temperature. Polymerization occurs
rapidly. Processes similar to the foregoing are described in U.S.
Pat. No. 3,554,966 and U.S. Pat. No. 5,693,227.
[0090] A fluorinated ether of aromatic acid can also be polymerized
with the trihydrochloride-monohydrate of tetraminopyridine in a
condensation polymerization in strong polyphosphoric acid under
slow heating above 100.degree. C. up to about 180.degree. C. under
reduced pressure, followed by precipitation in water, as disclosed
in U.S. Pat. No. 5,674,969 (which is incorporated in its entirety
as a part hereof for all purposes); or by mixing the monomers at a
temperature from about 50.degree. C. to about 110.degree. C., and
then 145.degree. C. to form an oligomer, and then reacting the
oligomer at a temperature of about 160.degree. C. to about
250.degree. C. as disclosed in U.S. Provisional Application No.
60/665,737, filed Mar. 28, 2005 (which is incorporated in its
entirety as a part hereof for all purposes), published as WO
2006/104974. The polymer that may be so produced may be a
pyridobisimidazole-2,6-diyl(2,5-dialkoxy-p-phenylene) polymer or a
pyridobisimidazole-2,6-diyl(2,5-diareneoxy-p-phenylene) polymer
such as a poly(1,4-(2,5-diareneoxy)phenylene-2,6-pyrido[2,3-d:
5,6-d']bisimidazole) polymer. The pyridobisimidazole portion
thereof may, however, be replaced by any one or more of a
benzobisimidazole, benzobisthiazole, benzobisoxazole,
pyridobisthiazole and a pyridobisoxazole; and the
2,5-dialkoxy-p-phenylene portion thereof may be replaced by an
alkyl or aryl ether of one or more of isophthalic acid,
terephthalic acid, 2,5-pyridine dicarboxylic acid, 2,6-naphthalene
dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 2,6-quinoline
dicarboxylic acid, and 2,6-bis(4-carboxyphenyl)pyridobisimidazole,
wherein such a fluorinated ether is produced according to the
methods disclosed herein.
[0091] The polymer prepared in such manner may, for example,
contain one or more of the following units:
[0092] pyridobisimidazole-2,6-diyl(2,5-dialkoxy-p-phenylene) and/or
pyridobisimidazole-2,6-diyl(2,5-diphenoxy-p-phenylene) units;
[0093] units selected from the group consisting of
pyridobisimidazole-2,6-diyl(2,5-dimethoxy-p-phenylene),
pyridobisimidazole-2,6-diyl(2,5-diethoxy-p-phenylene),
pyridobisimidazole-2,6-diyl(2,5-dipropoxy-p-phenylene),
pyridobisimidazole-2,6-diyl(2,5-dibutoxy-p-phenylene) and
pyridobisimidazole-2,6-diyl(2,5-diphenoxy-p-phenylene);
[0094] pyridobisthiazole-2,6-diyl(2,5-dialkoxy-p-phenylene) and/or
pyridobisthiazole-2,6-diyl(2,5-diphenoxy-p-phenylene) units;
[0095] units selected from the group consisting of
pyridobisthiazole-2,6-diyl(2,5-dimethoxy-p-phenylene),
pyridobisthiazole-2,6-diyl(2,5-diethoxy-p-phenylene),
pyridobisthiazole-2,6-diyl(2,5-dipropoxy-p-phenylene),
pyridobisthiazole-2,6-diyl(2,5-dibutoxy-p-phenylene) and
pyridobisthiazole-2,6-diyl(2,5-diphenoxy-p-phenylene);
pyridobisoxazole-2,6-diyl(2,5-dialkoxy-p-phenylene) and/or
pyridobisoxazole-2,6-diyl(2,5-diphenoxy-p-phenylene) units;
[0096] units selected from the group consisting of
pyridobisoxazole-2,6-diyl(2,5-dimethoxy-p-phenylene),
pyridobisoxazole-2,6-diyl(2,5-diethoxy-p-phenylene),
pyridobisoxazole-2,6-diyl(2,5-dipropoxy-p-phenylene),
pyridobisoxazole-2,6-diyl(2,5-dibutoxy-p-phenylene) and
pyridobisoxazole-2,6-diyl(2,5-diphenoxy-p-phenylene);
[0097] benzobisimidazole-2,6-diyl(2,5-dialkoxy-p-phenylene) and/or
benzobisimidazole-2,6-diyl(2,5-diphenoxy-p-phenylene) units;
[0098] units selected from the group consisting of
benzobisimidazole-2,6-diyl(2,5-dimethoxy-p-phenylene),
benzobisimidazole-2,6-diyl(2,5-diethoxy-p-phenylene),
benzobisimidazole-2,6-diyl(2,5-dipropoxy-p-phenylene),
benzobisimidazole-2,6-diyl(2,5-dibutoxy-p-phenylene) and
benzobisimidazole-2,6-diyl(2,5-diphenoxy-p-phenylene);
[0099] benzobisthiazole-2,6-diyl(2,5-dialkoxy-p-phenylene) and/or
benzobisthiazole-2,6-diyl(2,5-diphenoxy-p-phenylene) units;
[0100] units selected from the group consisting of
benzobisthiazole-2,6-diyl(2,5-dimethoxy-p-phenylene),
benzobisthiazole-2,6-diyl(2,5-diethoxy-p-phenylene),
benzobisthiazole-2,6-diyl(2,5-dipropoxy-p-phenylene),
benzobisthiazole-2,6-diyl(2,5-dibutoxy-p-phenylene) and
benzobisthiazole-2,6-diyl(2,5-diphenoxy-p-phenylene);
[0101] benzobisoxazole-2,6-diyl(2,5-dialkoxy-p-phenylene) and/or
benzobisoxazole-2,6-diyl(2,5-diphenoxy-p-phenylene) units;
and/or
[0102] units selected from the group consisting of
benzobisoxazole-2,6-diyl(2,5-dimethoxy-p-phenylene),
benzobisoxazole-2,6-diyl(2,5-diethoxy-p-phenylene),
benzobisoxazole-2,6-diyl(2,5-dipropoxy-p-phenylene),
benzobisoxazole-2,6-diyl(2,5-dibutoxy-p-phenylene) and
benzobisoxazole-2,6-diyl(2,5-diphenoxy-p-phenylene).
EXAMPLES
[0103] The advantageous attributes and effects of the processes
hereof may be seen in laboratory examples, as described below. The
embodiments of these processes on which the example is based are
representative only, and the selection of those embodiments to
illustrate the invention does not indicate that conditions,
arrangements, approaches, steps, techniques, configurations or
reactants not described in the example are not suitable for
practicing these processes, or that subject matter not described in
the example is excluded from the scope of the appended claims and
equivalents thereof.
Materials.
[0104] All reagents were used as received.
1,2-bis(methylamino)cyclohexane (97% purity), sodium hydride (95%
purity). 2,2,2-Trifluoroethanol (99% purity), triphenylphosphine
(99% purity), and diethyl diazodicarboxylate, (97+% purity) were
obtained from Sigma-Aldrich (Milwaukee, Wis., USA).
2,5-dibromoterephthalic acid (98+% purity) was prepared according
to the procedure in described in WO 2008/082501. Copper(II) bromide
("CuBr.sub.2"), dimethyl 5-hydroxyiosphthalate (98% purity), and
1H, 1H, 2H, 2H-perfluorooctanol (97% purity) were obtained from
Alfa Aesar (Ward Hill, Mass., USA). was obtained from (Milwaukee,
Wis., USA). 2,2,3,3-Tetrafluoropropanol was of 99% purity.
[0105] The meaning of abbreviations is as follows: "DEAD" means
diethyl azodicarboxylate, "eq" means equivalent(s), "g" means
gram(s), "GC" means gas chromatography, "mL" means milliliter(s),
"mmol" means millimole(s), "N" means normal, and "NMR" means
nuclear magnetic resonance spectroscopy, "PPh.sub.3" means
triphenyl phosphine, and "THF" means tetrahydrofuran.
##STR00034##
Example 1
Preparation of 2,5-bis(2,2,2-trifluoroethoxy)terephthalic acid
[0106] To a solution of 8 mL 2,2,2-trifluoroethanol
(CF.sub.3CH.sub.2OH) in 15 mL of THF was carefully added 0.19 g
(7.9 mmol) of sodium hydride. When gas evolution was complete,
0.488 g (1.5 mmol) of 2,5-dibromoterephthalic acid was added to the
solution, followed by addition of a solution of CuBr.sub.2 (0.092
mmol) and 1,2-bis(methylamino)cyclohexane (0.19 mmol) in 1.5 mL of
CF.sub.3CH.sub.2OH. The resulting pale blue slurry was heated at
60.degree. C. for four days. Aqueous HCl (1 N) was added to
precipitate the product. The product was washed with water, then
dissolved in methanol, and the resulting solution was filtered. The
methanol was removed under vacuum to give the product as colorless
microcrystals. Yield: 0.384 g, 71%.
[0107] Elemental analysis: Calculated for
C.sub.12H.sub.8F.sub.6O.sub.6: C, 39.80%; H, 2.23%. Found: C,
39.93%, 2.31%.
[0108] NMR analysis: .sup.1H (CD.sub.3OD): 7.53 (s, 2H), 4.57 (q,
8.5 Hz, 4H)
[0109] .sup.13C (CD.sub.3OD): 167.7, 152.9, 128.2, 124.9 (q, 277
Hz), 120.4, 69.1 (q, 35.4 Hz).
Example 2
Preparation of 2,5-bis(2,2,3,3-tetrafluoropropoxy)terephthalic
acid
[0110] A flask was charged with 5 mL of anhydrous THF and 8.1 mmol
of sodium hydride. A solution of 1.5 g (11.4 mmol) of
2,2,3,3-tetrafluoropropanol (HCF.sub.2CF.sub.2CH.sub.2OH) in 5 mL
of THF was added dropwise. When gas evolution was complete,
2,5-dibromoterephthalic acid (1.51 mmol) was added to the colorless
solution. Next, a mixture of CuBr.sub.2 (0.13 mmol) and
1,2-bis(methylamino)cyclohexane (0.22 mmol) in 0.5 g of
HCF.sub.2CF.sub.2CH.sub.2OH was added to the solution. The
resulting pale blue slurry was heated at 60.degree. C. for two
days. The product was isolated by treating the cooled reaction
product with 0.5 N HCl, then with water, and washing the
precipitate with water. Yield: 0.465 g, 72%.
[0111] NMR analysis: .sup.1H (CD.sub.3OD): 7.56 (s, 2H), 6.39 (tt,
52.8 and 5.7 Hz, 2H), 4.52 (tt, 12.0 and 1.3 Hz, 4H).
Example 3
Preparation of dimethyl
5-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxy)isophthalate
##STR00035##
[0113] To a 3 neck 100 mL round bottom flask fitted with a stir
bar, addition funnel, and a thermocouple, under nitrogen, was added
dimethyl 5-hydroxyisophthalate (1.0 g, 0.0048 mol, 1.0 eq) and dry
tetrahydrofuran (25 mL). The reaction was cooled to -5.degree. C.,
followed by the addition of triphenylphosphine (1.5 g, 0.0057 mol,
1.2 eq), 1H,1H,2H,2H-perfluorooctanol (2.1 g, 0.0057 mol, 1.2 eq),
then by the dropwise addition of a solution of diethyl
azodicarboxylate (DEAD) (1.0 g, 0.0057 mol, 1.2 eq) in 5 mL of dry
tetrahydrofuran. The DEAD addition was slightly exothermic
(-5.degree. C. to 5.degree. C.). The cold bath was removed and the
reaction was stirred overnight at ambient temperature.
[0114] After approximately 16 hours, GC analysis showed partial
conversion of the dimethyl 5-hydroxyisophthalate (22%) and
formation of the desired product. Unreacted PPh.sub.3 and
1H,1H,2H,2H-perfluorooctanol were also observed. The product was
isolated by flash column chromatography (silica gel 60,
dichloromethane-hexanes) as a colorless oil in 35% yield based on
unreacted dimethyl 5-hydroxyisophthalate
[0115] NMR (CDCl.sub.3): .sup.1H, 8.32 (s, 1H), 2.05 (s, 2H), 4.36
(m, 2H), 3.95 (s, 6H), 2.67 (m, 2H). .sup.13C (carbons with direct
fluorine attachment omitted): 166.0 (s), 158.3 (s), 132.1 (s),
123.8 (s), 119.8 (s), 60.7 (s), 52.5 (s), 31.3 (t, J.sub.CF=22 Hz).
MS: M.sup.+ (556 amu), M-OCH.sub.3.sup.+ (525 amu),
M-CO.sub.2CH.sub.3.sup.+ (497 amu).
[0116] In this specification, each of the formulae shown herein
describes each and all of the separate, individual compounds that
can be formed in that formula by (1) selection from within the
prescribed range for one of the variable radicals, substituents or
numerical coefficients while all of the other variable radicals,
substituents or numerical coefficients are held constant, and (2)
performing in turn the same selection from within the prescribed
range for each of the other variable radicals, substituents or
numerical coefficients with the others being held constant. In
addition to a selection made within the prescribed range for any of
the variable radicals, substituents or numerical coefficients of
only one of the members of the group described by the range, a
plurality of compounds may be described by selecting more than one
but less than all of the members of the whole group of radicals,
substituents or numerical coefficients. When the selection made
within the prescribed range for any of the variable radicals,
substituents or numerical coefficients is a subgroup containing (i)
only one of the members of the whole group described by the range,
or (ii) more than one but less than all of the members of the whole
group, the selected member(s) are selected by omitting those
member(s) of the whole group that are not selected to form the
subgroup. The compound, or plurality of compounds, may in such
event be characterized by a definition of one or more of the
variable radicals, substituents or numerical coefficients that
refers to the whole group of the prescribed range for that variable
but where the member(s) omitted to form the subgroup are absent
from the whole group.
[0117] Where a range of numerical values is recited herein, the
range includes the endpoints thereof and all the individual
integers and fractions within the range, and also includes each of
the narrower ranges therein formed by all the various possible
combinations of those endpoints and internal integers and fractions
to form subgroups of the larger group of values within the stated
range to the same extent as if each of those narrower ranges was
explicitly recited. Where a range of numerical values is stated
herein as being greater than a stated value, the range is
nevertheless finite and is bounded on its upper end by a value that
is operable within the context of the invention as described
herein. Where a range of numerical values is stated herein as being
less than a stated value, the range is nevertheless bounded on its
lower end by a non-zero value.
[0118] In this specification, unless explicitly stated otherwise or
indicated to the contrary by the context of usage, amounts, sizes,
ranges and other quantities and characteristics recited herein,
particularly when modified by the term "about", may but need not be
exact, and may also be approximate and/or larger or smaller (as
desired) than stated, reflecting tolerances, conversion factors,
rounding off, measurement error and the like, as well as the
inclusion within a stated value of those values outside it that
have, within the context of this invention, functional and/or
operable equivalence to the stated value.
[0119] Where an embodiment of this invention is stated or described
as comprising, including, containing, having, being composed of or
being constituted by certain features, it is to be understood,
unless the statement or description explicitly provides to the
contrary, that one or more features in addition to those explicitly
stated or described may be present in the embodiment. An
alternative embodiment of this invention, however, may be stated or
described as consisting essentially of certain features, in which
embodiment features that would materially alter the principle of
operation or the distinguishing characteristics of the embodiment
are not present therein. A further alternative embodiment of this
invention may be stated or described as consisting of certain
features, in which embodiment, or in insubstantial variations
thereof, only the features specifically stated or described are
present.
* * * * *